Process of producing quaternary ammonium compounds



' 30 conditions by Working in a closed vessel. The 130 p t Of 1 Cent Sulphuric acid and the Patented Nov. 22, 1938 h r 2,137,314

PROCESS OF PRODUCING QUATERNARY AMIVIONIUM COMPOUNDS Heinrich Ulrich and Ernst Ploetz, Ludwigshafenon-the-Rliine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankforton-the-Main, Germany No Drawing. Application May '7, 1936, Serial No 78,410. in Germany May 22, 1935 13 Elaims. (Cl. 260-584) The present invention relates to a process of one high molecular aliphatic radicle are especially producing quaternary ammonium compounds. valuable for many purposes.

We have found that quaternary ammonium The following examples will further illustrate compounds can be prepared in an advantageous the nature of this invention but the invention is 5 manner by causing alkylene oxides to act under not restricted to these examples. The parts are a pressure above atmospheric pressure on salts by Weight. of a nitrogenous base, i. e., ammonia or of amines. Emample 1 The reaction may be carried out in the absence of water, anhydrous salts of the quaternary ammonium bases thus being directly obtained by a smooth reaction. Temperatures up to'about 100 C. are usually very satisfactory. For example the quaternary salts are formedwithin a short time merely by heating at from about 50 to 100 C. The reaction may also be carried out in the presence of water. n

It is preferable to employ amounts of alkylene oxides which arev approximately equal to those Example 2 theoretically necessary for the preparation of the all quaternary compounds, or a light excfass over 1200 parts of triethanolamine are neutralized 2 such amounts; when. starting from tertiary With 320 Parts Of 43 p Cent Sulphuric acid amines, 1 molecular proportion of alkyiene oxide healedtogellhel with parts of ethylene flxlde or slightly more should advantageously be emin an autoclave at fmm m 1000 ployed for 1 molecular proportion of amine, in 06 8 Pressure s n0 longer P RS t- After l" .25 the case of secondary amines, 2 molecular pro- (imtion, 1979 D 0 & -C -c ys 2-) portions of alkylene oxide or a slight excess over lizing P1091116?- Of & y py nature are Obtamed 560 parts of triethanolamine hydrochloride andliO parts of ethylene oxide are heated to w 100 C. in an autoclave. After heating for two hours, all the ethylene oxide has entered into reaction. A syrupy crystal pulp is obtained which solidifies completely after standing for some time and which consists to the extent of 15} about 86 per cent of tetra-ethanolammonium chloride. A little unchanged initial material is also present.

this amount should b u d, d so on which still contains unconverted triethanol Generally speaking the increased pressure is amine in the form the free baseemployed which is produced under the reaction If the resulting Product be mutrallzed with pressure may, however, be still further increased product be reacted under the above Q by pressing" in inert gases, as for example nitrowith further 50 parts of e y efl 1t 15 possible to convert 95 per cent of the triethanol- The salts of ammonia or of primary, secondary amine p e into the quaternary ammlmium 3..- or tertiary amines with organic acids, such as Compound acetic, butyric or stearic acid or inorganic acids, Examp e 3 for example strong inorganic acids such as hydrochloric or sulphuric acid are suitable for carrying out the reaction. The amines may con- 1550 parts of triethanolamine sulphate and 400 parts of ethylene oxide are heated. together in an autoclave at from 60 to 70 C. until excess to tain one or more hydroxyalkyl radicles or may pressure can no longer be detected 1900 parts 4 be free from such radicl es. The salts of amines of a Walter-18m mass of syrupy consistency are ggg g i g agg fi z ggg gggggiggfigg; obtained. By reacting with barium hydroxide, be fr fro; resalting quaternary filtering oft the barium sulphate, and concentrate-j monium Salts ing the filtrate, the free base is obtained.

The products obtained which are quaternary per cent of tnethanolamme employed has ammonium compounds containing at least one been converted Into tetriethaml ammonium hy' hydroxyavlkyl group may be employed for ex" droxide; there is also still some triethanolamine ample as valuable assistants for the textile and present like industries, as dyestufi intermediates, or for Emmpze 4 50 pharmaceutical purposes. By starting from 430 parts of triethanolamine stearate and 50 suitable amines, products may also be obtained parts of ethylene oxide are heated under pressure which may be employed as dyestufis. The quatat 90 C. The reaction is completed after 2 to 3 ernar ammonium compounds obtainable accordhours. The tetraethanol ammonium stearate 05 ing to the present invention containing at least formed is readily soluble in water. In alcohol it reacts neutral to phenol-phthalein, while the stearic acid contained in triethanolamine stearate when dissolved in alcohol is capable of titration with caustic soda using phenol-phthalein as indicator.

Example 5 300 parts of the triethanolamine salt of acid octodecyl sulphuric ester are stirred with 400 parts of water and heated with 50 parts of ethylene oxide at from 50 to 60 C. under pressure. The tetra-ethanol ammonium salt is more readily soluble than the initial material and has a neutral reaction in water and in alcohol.

Example 6 300 parts of a 20 per cent solution of trimethylamine are neutralized with 100 parts of concentrated hydrochloric acid and treated for 3 hours with 50 parts of ethylene oxide under pressure at 60 C. After the said period, all the ethylene oxide has been absorbed. 450 parts of a solution are obtained which has a neutral reaction in alcohol. Choline hydrochloride has been formed in practically a quantitative yield.

Example 7 '73 parts of diethylamine are neutralized with 200 parts of 24 per cent sulphuric acid and heated in an autoclave at 60 C. with 100 parts of ethylene oxide. By adding 150 parts of barium hydroxide to the resulting solution, the base is set free. About 96 per cent of the diethylamine employed have been converted into the diethyldiethanol ammonium compound.

Example 8 500 parts of ammonium sulphate, 500 parts of water and 1350 parts of ethylene oxide are heated in an autoclave at from to 100 C. After some hours, the reaction is completed. The resulting solution is freed from sulphuric acid by means of 1200 parts of barium hydroxide. The product contains more than 50 per cent or tetraethanol ammonium hydroxide.

Example 9 245 parts of a mixture of tertiary amines each of which contains two methyl groups 'and an alkyl radicle of high molecular weight which corresponds to the alcohols obtainable by the reduction of palm kernel fatty acids, are stirred with 500 parts of water and neutralized with 200 parts oil 25 per cent sulphuric acid. The resulting solution is heated in a pressure vessel with 50 parts of ethylene oxide at from 90 to 100 C. All the ethylene oxide is absorbed within an hour. 1000 parts 01' an about 34 per cent solution of a quaternary ammonium sulphate containing two methyl groups, an ethanol group and an alkyl group of high molecular weight of the above type are obtained.

Example 10 107 parts of ammonium chloride are heated in a closed vessel together with 360 parts of ethylene oxide at 80 C. until the reaction is completed. A syrupy mass is obtained which contains 96 per cent or the theoretical amount of the quaternary organic ammonium compound iormed.

Example 12 270 parts oi. a 32 per cent aqueous solution of morpholine are neutralized with 100 parts of concentrated hydrochloric acid. The solution formed is heated with parts of ethylene oxide in an autoclave at from 70 to 80 C. until practically ordinary pressure prevails in the autoclave. The clear colorless solution obtained contains the quaternary ammonium compound formed in a good yield.

What we claim is: I

1. The process of producing quaternary ammonium compounds which comprises causing an alkylene oxide to react in a closed vessel with a salt of a nitrogenous base said base being selected from the group consisting of ammonia and amines and said alkylene oxide being employed in an amount about equal to that theoretically required for the production of an alkylolquaternary ammonium compound from the base employed.

2. The process of producing quaternary ammonium compounds which comprises causing an alkylene oxide to react at a temperature up to about in a closed vessel with a salt of a nitrogenous base said base being selected from the group consisting of ammonia and amines and said alkylene oxide being employed in an amount about equal to that theoretically required for the production of an alkylol quarternary ammonium compound from the base employed.

3. The process of producing quaternary ammonium compounds which comprises causing ethylene oxide to react in a closed vessel with a salt 01 a nitrogenous base said base being selected from the group consisting of ammonia and amines and said ethylene oxide being employed in an. amount about equal to that theoretically required for the production of an ethylol quaternary ammonium compound Irom the base employed.

4. The process of producing quaternary ammonium compounds which comprises causing ethylene oxide to react at a temperature up to about 100 C. in a closed vessel with a salt of a nitrogenous base said base being selected from the group consisting of ammonia and amines and said ethylene oxide being employed in an amount about equal to that theoretically required for the production of an ethylol quaternary ammonium compound Irom the base employed.

5. The process-oi producing quaternary ammonium compounds which comprises causing about the amount of ethylene oxide theoretically necessary for producing the quaternary compound to react at a temperature up to about 100 C. in a closed vessel with a salt or a nitrogenous base said base being selected from the group consisting of ammonia and amines and said ethylene oxide being employed in an amount about equal to that theoretically required for the production of an ethylol quaternary ammonium compound from the base employed.

6. The process of producing quaternary ammonium compounds which comprises causing an alkylene oxide to react in a closed vessel with a salt 01' an amine with a strong acid said alkylene oxide being employed in an amount about equal to that theoretically required for the production of an alkylol quaternary ammonium compound irom the amine employed.

7. The process of producing quaternary ammonium compounds which comprises causing an alkylene oxide to reactin a closed vessel ,with-an ammonium salt of a strong acid said alkylene oxide being employed in an amount about equal to that theoretically required for. the production 0! an alkylol quaternary ammonium compound from the ammonium salt employed.

8. The process oi. producing quaternary ammonium compounds which comprises causing ethylene oxide to react at a temperature up to about 100 C. in a closed vessel with an ammonium salt of a strong inorganic acid said ethylene oxide being employed in an amount about equal to that theoretically required for the production of an ethylol quaternary ammonium compound from the ammonium salt employed.

9. The process of producing quaternary ammonium compounds which comprises causing ethylene oxide to react at a temperature up to about 100 C. in a closed vessel with a salt of an amine with a strong inorganic acid said'ethyl- 85 ene oxide being employed in an amount about equal to that theoretically required tor the pro-- ,duction of an ethylol quaternary ammonium compound from the ammonium salt employed.

10. Tetraethanolammoniumstearate.

11. The tetraethanolammonium salt of the acid octodecyl sulphuric ester.

12. Quaternary ammonium compounds corresponding to the formula in which R1 represents an alkylol group, R: a high molecular aliphatic radicle the carbon atoms of which are directly attached to one another, R3 and R4 are low molecular aliphatic sponding to the formula wherein R1, R2. R: man. are aliphatic radicles at least one of which is an alkylol radicle and at least one of which is high molecular, the remainin: ones being low molecular and tree from double linkages, and wherein X representsan anion.

' HEINRICH ULRICH.

ERNST PLOETZ. 

